Amides

ABSTRACT

This invention described in this patent application relates to novel amides of the formula (I) ##STR1## wherein the substituents are as defined in the disclosure, intermediates for such amides, synthesis thereof and their use for the control of weeds.

This invention relates to novel amides, intermediates therefore,synthesis thereof, and the use of said compounds for the control of Moreparticularly, one aspect of this invention relates to a compound of theformula (I) ##STR2## wherein

R is H, C₁₋₃ alkyl or C₂₋₃ alkenyl optionally substituted by halo; or isC₂₋₃ alkinyl;

R₁ is phenyl(C₁₋₄ alkyl)_(n), wherein the phenyl group is optionallysubstituted by one or more groups selected from --C(O)--O--C₁₋₄ alkyl,C₁₋₈ alkyl, C₁₋₈ haloalkyl, halo, nitro, cyano, --SO₂ C₁₋₄ alkyl, SO₂NR₅ R₅ ' and S(O)NR₅ R₅ '; or is C₅₋₈ cycloalkenyl; --N═R₆ ; C₂₋₈alkenyl, C₁₋₈ alkyl or C₃₋₅ alkinyl optionally substituted with one ormore halo; or is C₁₋₄ alkyl--SO₂ --C₁₋₄ alkyl;

R₂ is halo or hydrogen;

R₃ is halo, cyano or C₁₋₄ alkyl;

R₄ is H; NO₂ ; NH₂ ; CN; C₁₋₈ alkyl optionally substituted by CN; C₂₋₈alkenyl optionally substituted by CN; C₂₋₅ alkinyl; (C₂₋₅alkoxycarbonyl)-C₁₋₄ alkyl, whereby the carbon atom of the alkyl groupalpha to the alkoxycarbonyl group may bear one more C₂₋₅ alkoxcarbonylgroups or a cyano group; (C₂₋₅ alkoxycarbonyl)-C₋₄ alkoxy-C₁₋₄ alkyl;(C₂₋₅ alkoxycarbonyl)-C₁₋₄ alkylamino-C₁₋₄ alkyl; (C₂₋₅alkoxycarbonyl)-C₂₋₅ alkenyl, whereby the alkenyl moiety is optionallysubstituted by halogen; C₁₋₄ alkylthio-C₁₋₄ alkyl; C₁₋₄alkylsulfonyl-C₁₋₄ alkyl; C₁₋₄ alkoxy-C₁₋₄ alkoxy; X(Alk)_(m) R₇ ;OCH(SR₈)-COOR₉ ; NR₁₀ R₁₁ ; COOR₁₂ ; CONR₁₃ R₁₃ '; COR₁₄ or R₁₅ ;

or R₃ and R₄ join together with the phenyl ring to form a bicyclic ringcontaining nine to ten ring atoms, one to three of said ring atomsoptionally being selected from oxygen, nitrogen and sulfur, andoptionally being substituted with one or more groups selected from C₃₋₈alkinyl, C₁₋₈ alkyl, halo, oxo, C₁₋₄ alkylene-R₁₆, and C₂₋₈ alkenyl;

R₅ and R₅ ' independently are C₁₋₄ alkyl;

R₆ is C₂₋₈ alkylidene;

R₇ is H; C₁₋₄ alkyl, C₂₋₅ alkenyl C₂₋₅ alkinyl, or C₃₋₈ cycloalkyl,which hydrocarbyl is unsubstituted or substituted by one or more halogenor by CN; cyclopentanonyl; phenyl optionally substituted byO--Alk'--COOR₈ ; or is C₂₋₅ alkanoyl; C₂₋₅ alkoxycarbonyl; C₂₋₈(alkoxycarbonyl)(C₃₋₈ cycloalkyloxy)carbonyl, in which the alkoxy orcycloalkyloxy group is optionally substituted by one or more halo; CONR₉R₈ ', C(═NOR₈)--COOR₈ ', CN; P(O)(OR₈)(OR₈ ') or R₁₅ ;

R₈ and R₈ ', independently are C₁₋₄ alkyl;

R₉ is C₁₋₄ alkyl optionally substituted by one or more halo;

R₁₀ is H or C₁₋₄ alkyl;

R₁₁ is H; C₁₋₄ alkyl, optionally substituted by P(O)(OR₈)(R₈ '); C₂₋₅alkanoyl; C₂₋₅ alkoxycarbonyl; or C₂₋₅ alkoxycarbonyl-C₁₋₄ alkyl;

R₁₂ is N═(C₂₋₈ alkylidene); C₁₋₄ alkyl optionally substituted by one ormore groups selected from halo, C₁₋₄ alkoxy, tri-C₁₋₄ alkylsilyloxy,tri-C₁₋₄ alkyl-silyl, (tri-C₁₋₄ alkylsilyloxy)-carbonyl, C₂₋₅alkoxycarbonyl, P(O)(OR₈)(OR₈ '), C₂₋₅ alkanoyl-oxy or by di(C₁₋₄alkylamino)-carbonyloxy in which both alkyl groups may be tied togetherto form a saturated 5 to 6 membered heteroring optionally containing onefurther heteroatom selected from O, S and N, and in which any furtherN-heteroatom present may, depending on the hydrogenation degree of theheteroring, bear a hydrogen or a C₁₋₄ alkyl group;

R₁₃ is H or C₁₋₄ alkyl;

R₁₃ ' is H, C₁₋₄ alkyl optionally substituted by halo, C₁₋₄ alkoxy,phenyl, CHO, C₂₋₅ alkanoyl, C₁₋₄ alkylsulfonyl, (C₂₋₅alkoxycarbonyl)-C₁₋₄ alkyl or(C₂₋₅ alkoxycarbonyl)-C₁₋₄ alkoxy;

or R₁₃ and R₁₃ ' together form a 4 to 6 membered heteroring optionallycontaining one or two further heteroatoms selected from O, S and N,whereby, depending on the hydrogenation degree of the heteroring, anyfurther N-heteroatom may bear hydrogen or be substituted by C₁₋₄ alkyl;

R₁₄ is H or C₁₋₄ alkyl;

R₁₅ is a heterocyclic ring having 5 or 6 ring atoms, one to three ofsaid ring atom being selected from oxygen, sulfur and nitrogen, whichring is optionally substituted with one or more C₁₋₄ alkyl groups;

R₁₆ is CN; COOR₁₂ ; OC₁₋₄ alkyl; or is 4-tetrahydropyranyl,2H-5,6-dihydro-thiin-3-yl, 2-pyridyl, 2-pyrazinyl, 1,2-oxazol-3-yl, or1,2,4-oxdiazol-3-yl, each of which is optionally substituted with C₁₋₄alkyl;

Alk and Alk' independently are C₁₋₄ alkylene;

n and m independently are 0 or 1;

A is a C₃₋₄ alkylene or C₃₋₄ alkenylene straight chain optionallysubstituted by one to three halogen; or is a propylene or propenylenestraight chain interposed by a heteroatom or heterogroup selected fromS, O, SO, SO₂, and NR₁₀ ; and

X, Y and Z are independently selected from O and S.

Where R₁ is or contains a C₁₋₈ alkyl group or R₄ is a C₁₋₈ alkyl group,it is preferably a C₁₋₄ alkyl group. Any alkyl group may be branched orstraight chain.

Where R₁ is a C₂₋₈ alkenyl group, it is preferably a C₂₋₅ alkenyl group.Any alkenyl group may be either branched or straight chain.

Where the bicyclic ring formed by junction of R₃ and R₄ is substitutedby a C₃₋₈ alkinyl group, it is preferably a C₃₋₅ alkinyl group. Anyalkinyl groups may be either branched or straight chain.

Where R₁ is a C₅₋₈ cycloalkenyl group, it is preferably a C₅₋₆cycloalkenyl group.

Where R₇ contains a C₃₋₈ CYcloalkyl group, it is preferably a C₃₋₅cycloalkyl group.

Where R₁, R₄, R₇ or R₂ contains halogen, it is preferably chlorine orfluorine.

R₆ may be straight or branched chain; it may be cyclic or contain acycloalkyl group.

Where R₆ cycloalkylidene, it is preferably C₃₋₆ cycloalkylidine, morepreferably C₂₋₆ cycloalkylidene.

Where R₆ is branched or straight chain alkylidene it is preferably C₂₋₈alkylidene, more preferably C₂₋₅ alkylidene.

Where R₃ and R₄ join together with the phenyl ring to form a bicyclicring, it is preferably an indanone; a benzazinone, particularly aquinolinone; a benzoxazinone; a benzodiazinone particularlydihydroquinoxalinone; a benzothiazinone; a benzodioxane; a benzopyrane;a benzopyrone, particularly coumarin; a benzazole, particularly anindole, an indolone, an indazole, a benzotriazole, an isatine or abenzimidazolone; a benzoxazolone; a benzothiazolone; a benzofurane; or abenzdioxolane;

Where R₁, R₄, R₇, R₉, R₁₂, R₁₅ or A are substituted, they are preferablymono-, di- or tri-substituted.

X, Y and Z are preferably oxygen.

R is preferably H.

R₁ is preferably selected from phenyl optionally substituted withhalogen, nitro or CH₃ OC(O)--; C₁₋₄ alkyl optionally substituted withone to four halogen atoms; C₂₋₄ alkenyl; or C₂₋₃ alkylidene═N--.

R₂ is preferably chlorine or fluorine, more preferably fluorine.

R₃ is preferably CN, Br, Cl or methyl.

R₄ is preferably O(Alk)_(m) R₇, COOR₁₂ or CONR₁₃ R₃ ';

R₇ is preferably C₁₋₄ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkinyl, or C₂₋₅alkoxycarbonyl.

R₁₂ is preferably C₁₋₄ alkyl optionally substituted by halo.

R₁₃ is preferably H.

R₁₃ ' is preferably C₁₋₄ alkyl optionally substituted by halo.

R₁₅ is preferably an azole particularly pyrazol, triazol orbenzimidazol; thiophene; furane; oxadiazole; oxazoline; dioxolane;dithiolane; pyrane; or dihydro- or tetrahydrothiine; and is preferably aheteroring containing 1-3 heteroatoms.

A is preferably straight chain butylene substituted by fluorine.

Alk is preferably CH₂ or CH(CH₃);

Compounds of the formula (I) may be prepared by reacting a compound ofthe formula (II) ##STR3## with a compound of the formula (III) ##STR4##wherein R--R₄, A, X, Y and Z are as previously defined and W₁ ishalogen.

This reaction is suitably carried out at 0°-50° C. in an inert solventsuch as methylene chloride, chloroform, acetone, acetonitrile or etherin the presence of a base such as triethylamine, sodium carbonate orpotassium carbonate. The compound of the formula (I) may be recoveredfrom solution by standard techniques, such as liquid-liquid phaseseparation, and subsequent evaporation in vacuo.

Compounds of the formula (II) are believed to be novel, and form anotheraspect of this invention.

Compounds of the formula (II) can be prepared by reacting a compound ofthe formula (IV) ##STR5## with a compound of the formula (V) ##STR6##wherein A, Z, R and R₂₋₄ are as previoiusly defined and W₂ is halogen.

This reaction is exothermic and is suitably carried out at 0°-500° C. inan inert solvent as previously mentioned. After the reaction subsides, asuitable base, as previously mentioned, is added, after which thereaction mixture is stirred. The compound of the formula (II) may berecovered from solution by standard techniques, such as liquid-liquidphase separation, and subsequent evaporation in vacuo.

Compounds of the formulae (III), (IV) and (V) are known, or can beprepared according standard techniques from known compounds.

The compounds of formula (I) are useful because they control the growthof plants. By plants it is meant germinating seeds, merging seedlingsand established vegetation including underground portions. Inparticular, the compounds are useful as herbicides as indicated bycausing damage to both monocotyledoneous and dicotyledoneous plants invarious standard evaluations for determining such effects. Theherbicidal effects are exhibited both pre- and post-emergence theplants. Such herbicidal effects indicate that the compounds of formula(I) are particularly of interest in combatting weeds (unwanted plants).

The compounds of the formula (I) are indicated mainly to be strongeracting against dicotyledoneous plants than monocotyledoneous plants.Relatively less toxicity towards crops than towards weeds is furtherindicated. Hence, the compounds are of particular interest as selectiveherbicides to combat weeds in a crop locus, particularly as locus of acrop such as, for example, sugarbeet, sunflower, cotton soybean, cornand wheat.

The present invention therefore also provides a method of combattingweeds in a locus which comprises applying to the weeds or their locus aherbicidally effective amount of a compound of the invention. Whenselective action is desired in crop locus, the amount applied will besufficient to combat weeds without substantially damaging the crop.

For general herbicidal as well as selective herbicidal use of thecompounds of the invention, the particular amounts to be applied willvary depending upon recognized factors such as the compound employed,the plants primarily in the locus, the timing, mode and formulation inapplication, the various conditions of treatment such as soil andweather and the like. However, in general, satisfactory results in weedcontrol are usually obtained upon application of the compounds of theinvention at a rate in the range of from 0.01 to 10 kg/hectare, moreusually 0.05 to 2 kg/hectare, and preferably 0.1 to 1 kg/hectare, theapplication being repeated as necessary. When used in crops, theapplication usually will not exceed about 5 kg/hectare, and is usuallyin the range of 0.01 to 1 kg/hectare.

For practical use as herbicides, the compounds of formula (I) may be andare preferably employed in herbicidal compositions comprising aherbicidal effective amount of the compound and an inert carier which isagriculturally acceptable in the sense of not, by reason of itspresence, poisoning the agricultural environment including the immediatesoil of application or any crops present therein or otherwise beingunsafe for application. Such compositions of formulations may contain0.01% to 99% by weight of active ingredient, from 0 to 20% by weight ofagriculturally acceptable surfactants and 1 to 99.99% by weight of theinert carrier. Higher ratios of surfactant to active ingredient aresometimes desirable and are achieved by incorporation into theformulation or by tank mixing. Application forms of compositiontypically contain between 0.01 and 25% by weight of active ingredient,but lower or higher levels of active ingredient can, of course, bepresent depending on the intended use and the physical properties of thecompound. Concentrate forms of composition intended to be diluted beforeuse generally contain between 2 and 90%, preferably between 10 and 80%by weight of active ingredient.

Useful compositions or formulations of the compounds of the inventioninclude dusts, granules, pellets, suspension concentrates, wettablepowders, emulsifiable concentrates and the like. They are obtained byconventional manner, e.g. by mixing the compounds of the invention withthe inert carrier. More specifically, liquid compositions are obtainedby mixing the ingredients, fine solid compositions by blending and,usually grinding, suspensions by wet milling and granules and pellets byimpregnating or coating (preformed) granular carriers with the activeingredient or by agglomeration techniques.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as talc, clay, silica and thelike. Granular formulations can be prepared by impregnating thecompound, usually dissolved in a suitable solvent, onto and intogranulated carriers such as the attapulgites or the vermiculites,usually of a particle size range of from about 0.3 to 1.5 mm. Wettablepowders, which can be dispersed in water or oil to any desiredconcentration of the active compound, can be prepared by incorporatingwetting agents into concentrated dust compositions.

Alternatively, the compounds of the invention may be used inmicro-encapsulated form.

Agriculturally acceptable additives may be employed in the herbicidalcompositions to improve the performance of the active ingredient and toreduce foaming, caking and corrosion. Surfactant as used herein meansagriculturally acceptable material which imparts emulsifiability,spreading, wetting, dispersiblity or other surface-modifying propertiesproperties. Examples of surfactants are sodium lignin sulphonate andlauryl sulphate.

Carriers as used herein mean a liquid or solid material used to dilute aconcentrated material to a usable or desirable strength. For dusts orgranules it can be e.g. talc, kaolin or diatomaeous earth, for liquidconcentrate forms, a hydrocarbon such as xylene or an alcohol such asisopropanol; and for liquid application forms, e.g. water or diesel oil.

The compositions of this application can also comprise other compoundshaving biological activity, e.g. compounds having similar orcomplementary herbicidal ativity or compounds having antidotal,fungicidal or insecticidal activity.

Typical herbicidal composition, according to this invention, areillustrated by the following Examples A, B and C in which the quantitiesare in parts by weight.

EXAMPLE A Preparation of a Dust

10 Parts of a compound of formula (I) and 90 parts of powdered talc aremixed in a mechanical grinder-blender and are ground until ahomogeneous, free-flowing dust of the desired particle size is obtained.This dust is suitable for direct application to the site of the weedinfestation.

EXAMPLE B Preparation of Wettable Powder

25 Parts of a compound of formula (I) are mixed and milled with 25 partsof synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts ofsodium ligninsulphonate and 45 parts of finely divided kaolin until themean particle size is about 5 micron. The resulting wettable powder isdiluted with water before use to a spray liquor with the desiredconcentration.

EXAMPLE C Preparation of Emulsifiable Concentrate (EC)

13.37 Parts of a compound are mixed in a beaker with 1.43 parts ofToximul 360A (a mixture of anionic and non-ionic surfactants containinglargely anionic surfctants), 5.61 parts of Toximul 360A (a mixture ofanionic and non-ionic surfactants containing largely non-ionicsurfactants), 23.79 parts of dimethylformamide and 55.8 parts of Tenneco500-100 (predominantly a mixture of alkylated aromatics such as xyleneand ethylbenzene) until solution is effected. The resulting EC isdiluted with water for use.

FINAL COMPOUNDS EXAMPLE 1--12[[(4-chloro-2-fluoro-5-isopropoxyphenyl)amino]carbonyl]-1-piperidinecarboxylic acid-phenylester

To 15.6 g (0.05 mol) pipecolic acid 4-chloro-2-fluoro 5-isopropoxyanilide dissolved in 250 ml methylenchloride are added 5.5 g (0.054 mol)triethylamine. 7.8 g (0.05 mol) of phenylchloroformate are addeddropwise and the reaction mixture is stirred for 15 minutes at roomtemperature. 100 ml water is added and the organic layer is separated,washed with additional 100 ml water, dried (MgSO₄) and evaporated invacuo. The residue is homogenous by TLC (Rf═0.76 CH₂ --CH₂ /CH₃ OH,98:2)

In an analogous manner, the following compounds of formula (Ia) setforth in Table 1 are made.

                  TABLE 1                                                         ______________________________________                                         ##STR7##                     (Ia)                                            ______________________________________                                    

For compounds 1-2 through 1-184 and 221 through 227 Ar is 2-R₂ -4-R₃05-R₄ -phenyl.

For compounds 1-185 through 1-220, Ar is as indicated.

The orientation of the alkylene or alkenylene chain "A" set forth belowis such that the first carbon in the chain is bound to the nitrogen informula (Ia).

      Compd. R.sub.1 A X Y Z R.sub.2 R.sub.3 R.sub.4 mp °C. or R.sub.f     (silica gel)       1-2 phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2 CCH 130° C.     1-3 " " " " " " " H 82° C. 1-4 " " " " " " " OCH.sub.3 R.sub.f =     0,25 (CH.sub.2 CH.sub.2) 1-5 " " " " " " " OCH.sub.2 CH.sub.3 R.sub.f =     0,67(CH.sub.2 Cl.sub.2 /CH.sub.3      OH, 98:2) 1-6 " " " " " " " OCOOCH.sub.3 R.sub.f = 0,75 (Acetone) 1-7 "     " " " " " " OCH.sub.2CH.sub.2CH.sub.3 Rf = 0,65 (CH.sub.2 CH.sub.2     /CH.sub.3 OH, 98:2) 1-8 CH.sub.3 CH.sub.2 " " " " " " H 67° C.     1-9 " " " " " " " OCH.sub.3 R.sub.f = 0,13 (CH.sub.2 Cl.sub.2) 1-10 " "     " " " " " OCH(CH.sub.3).sub.2 R.sub.f = 0,55 (CH.sub.2 Cl.sub.2      /CH.sub.3 OH, 98:2) 1-11 benzyl " " " " " " OCH.sub.3 R.sub.f = 0,35     (CH.sub.2 Cl.sub.2) 1-12 " " " " " " " OCH(CH.sub.3).sub.2 118°     C. 1-13 CH.sub.3 " " " " " " " 92° C. 1-14 " CHCHSCH.sub.2 " " "     " " " 1-15 CH.sub.3 OCO-phenyl " " " " " " " R.sub.f = 0,54 (CH.sub.2     Cl.sub.2 /CH.sub.3 OH, 98:2) 1-16 CH.sub.3 OCO-phenyl " " " " " "     OCH.sub.2 CH.sub.2 CH.sub.3 R.sub.f = 0,59 (CH.sub.2 Cl.sub.2 /CH.sub.3     OH, 98:2) 1-17 CH.sub.3 OCO-phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2     CH.sub.3 R.sub.f = 0,56 (CH.sub.2 Cl.sub.2 /CH.sub.3 OH, 98:2) 1-18     phenyl " S " " " " OH(CH.sub.3).sub.2 103° C. 1-19 " " " " " " "     OCH.sub.2 CH.sub.2 CH.sub.3 105° C. 1-20 4-CH.sub.3 -phenyl " " "     " " " OCH(CH.sub.3).sub.2 100° C. 1-21 " " " " " " " OCH.sub.2     CH.sub.2 CH.sub.3 R.sub.f = 0,72 (CH.sub.2 Cl.sub.2 /CH.sub.3 OH, 98:2)     1-22 4-Cl-phenyl " " " " " " OCH(CH.sub.3).sub.2 135° C. 1-23 " "      O S " " " OCH(CH.sub.3).sub.2 R.sub.f = 0,64 (CH.sub.2 CH.sub.2     /CH.sub.3 OH, 98:2) 1-24 " " " O " " " " R.sub.f = 0,60 (CH.sub.2     Cl.sub.2 /CH.sub.3 OH, 98:2) 1-25 CH.sub.2CHCH.sub.2 " " " " " " "     R.sub.f = 0,69 (Acetone) 1-26 (CH.sub.3).sub.2 CHCHCl " " " "" " "     R.sub.f = 0,18 (CH.sub.2 Cl.sub.2) 1-27 Cl.sub.3 CCHCl " " " " " " "     55° C. 1-28 CH.sub.2CH " " " " " " " 92°      C. 1-29 (CH.sub.3).sub.2 CN " " " " " " " 56°      C. 1-30 (CH.sub.3).sub.2 CN (CH.sub.2).sub.4 O O O F Cl OC.sub.5     H.sub.9 -cycl. 154° 1-31 phenyl " " " " " " NH.sub.2 R.sub.f =     0,42 (ethyl acetate,          hereinafter Est/Hex, 1:1) 1-32 " " " " " "     F F 52° C. 1-33 "" " " " " Cl I 93° C. 1-34 " " " " " " "     OCCH.sub.3 R.sub.f =      0,45 (Est/Hex, 1:1) 1-35 " (CH.sub.2).sub.2SCH.sub.2 " " " " " OCH(CH.su     b.3).sub.2 105-105°; R.sub.f = 0,54 (Et.sub.2 O) 1-36 CH.sub.3 "     " " " " " " 83-84°; R.sub.f = 0,44 (Et.sub.2 O) 1-37 " " " " " "     " OCH(CH.sub.3) CH R.sub.f = 0.38 (Est-Hex 1:1) 1-38 (CH.sub.3).sub.2 CN (     CH.sub.2).sub.4 " " " " " OC.sub.4 H.sub.9 -sec 127° 1-39     4-Cl-phenyl CH.sub.2      CHCHCH.sub.2 " " " "" OCH(CH.sub.3).sub.2 93-95° 1-40 4-NO.sub.2     -phenyl (CH.sub.2).sub.3 " " " " " OC.sub.2 CCH 142°C. 1-41     4-Cl-phenyl " " " " " " " 144° C. 1-42 phenyl " " " " " " "     132° C. 1-43 " " " " " " " OCOOCH.sub.3 63° C. 1-44 "     (CH.sub.2).sub.2SCH.sub.2 " " " " " OCH.sub.3 121° 1-45 " " " " "     " " OC.sub.2 H.sub.5 R.sub.f = 0,49 (Est/Hex 1:1) 1-46 " " " " " " "     OC.sub.3 H.sub.7 -n R.sub.f = 0,51 (Est/Hex 1:1) 1-47 4-Cl-phenyl     (CH.sub.2).sub.2 CH(F)(CH.sub.2) O O O F Cl OCHCH.sub.3CCH 1-48 " " " "     " " " OCH(CH.sub.3).sub.2 1-49 " (CH.sub.2).sub.4 " " " " " OCH.sub.2     -phenyl 1-50 " " " " " " " OCH(CH.sub.3)phenyl 1-51 " " " " " " "     OCHCH.sub.3CH.sub.2 OCH.sub.3 1-52 " " " " " " " OCH.sub.2 COCH.sub.3     1-53 " " " " " " " OCH.sub.2 CHCH.sub.2 1-54 " " " " " " "  OCH.sub.2     CHCHCl 1-55 " " " " " " " OCH.sub.2 CClCH.sub.2 1-56 " " " " " " "     OCH.sub.2 -(2,2-di-Cl-         cyclopropyl) 1-57 " " " " " " " OCH.sub.2     -(2-Cl-cyclopropyl) 1-58 " " " " " " " OCH.sub.2 -cyclopropyl 1-59     phenyl (CH.sub.2).sub.2SCH.sub.2 " " " " " OC.sub.4 H.sub.9 -sec R.sub.f     = 0,56          (Est/Hex 1:1) 1-60 " " " " " " " OC.sub.4 H.sub.9 -cycl     134-135° 1-61 " " " " " " " OCH.sub.2 CCH 131-132° 1-62 "     " " " " " " OCH(CH.sub.3)CCH R.sub.f -0,27          (Est/Hex 1:3)     1-634-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2 CH.sub.2 OCH.sub.2     CH.sub.3 1-64 " " " " " " " OCH.sub.2 -(2-tetrahydrofuryl) 1-65 " " " "     " " " OCH.sub.2 -(2-tetrahydropyranyl) 1-66 " " " " " " " OCH.sub.2     -(2H-5,6-dihydrothiin-3-yl) 1-67 " " " " " " " OCHCH.sub.3COOEt 1-68 " "     " " " " " OCH.sub.2      CN 1-69 " " " " " " " OCH.sub.2C(NOCH.sub.3)COOC.sub.2 H.sub.5 1-70 " "     " " " " " OCH.sub.2 -(1,3-dioxolan-2-yl) 1-71 " " " " " " " OCH.sub.2     -(1,3-dithiolan-2-yl) 1-72 "  " " " " " " OCH.sub.2CO-(1,4-oxazin-4-yl)     1-73 " (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " " OCH.sub.2 COOC.sub.5     H.sub.11 -n 1-74 " (CH.sub.2).sub.4 " " " " " O-(-2-oxo-cyclopentyl)     1-75 " " " " " " " OPO(OCH.sub.3).sub.2 1-76 CH.sub.2CHCH.sub.3 (CH.sub.2     ).sub.2 CH(F)CH.sub.2 " " " " " OCH(CH.sub.3)CCH 1-77 " (CH.sub.2).sub.4     " " " " " OCH.sub.2 CHCH.sub.2 1-78 " " " " " " " OCHCH.sub.3COOCH.sub.2     CH.sub.3 1-79 4-Cl-phenyl " " " " " " OCH(SCH.sub.3)COOCH.sub.2 CH.sub.2     Cl      1-80 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl     ##STR8##       1-81 phenyl (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " " OCH.sub.2     CF.sub.3 1-82 " " " " " " " OCHF.sub.2 1-83 " " " " " " " OCH.sub.2     COO(cyclopentyl) 1-84 " " " " " " " OCH.sub.2 -(1-pyrazolyl) 1-85 " " "     " " " " 4-[C.sub.2 H.sub.5 OOCCH(CH.sub.3)O]-phenoxy 1-86 " " " " " " "     OCH.sub.2 -(2-thienyl) 1-87 " " " " " " " OCH(CH.sub.3)-(3-CH.sub.3     -1,2,4-oxadiazol-5-yl) 1-88 4-Cl-phenyl (CH.sub.2).sub.4 " " " Cl "     OCH(CH.sub.3).sub.2 1-89 " " " " " H " " 1-90 " (CH.sub.2).sub.2     CH(F)CH.sub.2 " " " F CH.sub.3 " 1-91 " " " " " " CN " 1-92 " " " " " "     CN OCH.sub.2 CCH 1-93 " (CH.sub.2).sub.4 " " " " Cl SCH(CH.sub.3).sub.2     1-94 " " " " " " " SCH.sub.2 CCH 1-95 " " " " " " " SCH.sub.2      COOCH.sub.2 CH.sub.3 1-96 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl     SCH(CH.sub.3)COOCH.sub.2 CH.sub.3 1-97 " " " " " " " SCH.sub.2 -phenyl     1-98 " " " " " " " S-(tetrahydro-2-pyranyl) 1-99 " " " " " " " NHCH.sub.2      COOCH.sub.2 CH.sub.3 1-100 " " " " " " " N(CH.sub.3).sub.2 1-101 " " "     " " " " NCH.sub.3COOCH.sub.2      CH.sub.3 1-102 " " " " " " " NHCOCH(CH.sub.3)CH.sub.2 CH.sub.3 1-103 "     " " " " " " NHCH(C.sub.2 H.sub.5)P(O)(C.sub.2 H.sub.5)(OC.sub.2 H.sub.5)     1-104 CH.sub.2CHCH.sub.3 " " " " " " SCH(CH.sub.3).sub.2 1-105 4-Cl-pheny     l " " " " " " COOCH(CH.sub.3).sub.2 1-106 " (CH.sub.2).sub.2      CH(F)CH.sub.2 " " " " " " 1-107 " (CH.sub.2).sub.2 CF.sub.2 CH.sub.2 "     " " " " " 1-108 " " " " " " " COOCH(CH.sub.2F).sub.2 1-109 " " " " " " "     COOCH.sub.2 CH.sub.2 OCH.sub.3 1-110 " " " " " " " COONC(CH.sub.3).sub.2     1-111 " " " " " " " COOCH.sub.2 CH.sub.2 -F 1-112 " (CH.sub.2).sub.4 " "     " " " COOCH.sub.2 CH.sub.2 OSi(CH.sub.3).sub.3 1-113 4-Cl-phenyl     (CH.sub.2).sub.4 O O O F Cl COOCH.sub.2 COOSi(CH.sub.3).sub.3 1-114 " "     " " " " " COOCH.sub.2      Si(CH.sub.3).sub.3 1-115 " " " " " " " COOCHCH.sub.3CH.sub.2      Si(CH.sub.3).sub.3 1-116 " " " " " " " COOCH.sub.2 CH.sub.2      PO(OCH.sub.3).sub.2 1-117 " " " " " " " COOCH(CH.sub.2      CH.sub.3)PO(OCH.sub.3).sub.2 1-118 " "  " " " " " COOCH.sub.2      COOCH.sub.2 CH.sub.3 1-119 " " " " " " " COOCH.sub.2 OCOCH.sub.3 1-120     " " " " " " " COOCH(CH.sub.3)OCO-piperidin-1-yl 1-121 " " " " " " "     CON(CH.sub.3).sub.2 1-122 " " " " " " " CONCH.sub.3OCH.sub.3 1-123 " " "     " " " " CONHSO.sub.2 CH.sub.3 1-124 " " " " " " " CONHOCH.sub.2 COOEt     1-125 " " " " " " " CONHCH.sub.2 COOEt 1-126 " " " " " " " CN 1-127 " "     " " " " " CHO 1-128 " " " " " " " COCH.sub.3 1-129 " "  " " " " "     4-COOC.sub.2 H.sub.5      -1,3-dioxolan-2-yl 1-130 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl     2-CH.sub.3      -1,3-dioxolan-2-yl 1-131 " " " " " " " 4,4-di(CH.sub.3)-4,5-dihydro-          1,3-oxazol-2-yl 1-132 " " " " " F CN COOCHCH.sub.3CH.sub.2 CH.sub.3     1-133 " " " " " F Cl CH.sub.3 1-134 " " " " " " " CH.sub.2      CH(CH.sub.3).sub.2 1-135 " " " " " " " CH.sub.2 COOCH.sub.2 CH.sub.3     1-136 " " " " " " " CH.sub.2 C(CN)(CH.sub.3)COOC.sub.2 H.sub.5 1-137 " "     " " " " " CH.sub.2 C(CH.sub.3)(COOC.sub.2 H.sub.5).sub.2 1-138 " " " " "     " " CH.sub. 2 OCH.sub.3 1-139 " " " " " " " CH.sub.2 OCH.sub.2 COOEt     1-140 " " " " " " " CH.sub.2 NHCH.sub.2 COOEt 1-141  " " " " " "     CH.sub.2 CH.sub.2 CN 1-142 " " " " " " " CH.sub.2 CH.sub.2 COOCH.sub.3     1-143 " " " " " " " CH.sub.2 CH(CH.sub.3)COOEt 1-144 " " " " " " "     CHCHCN 1-145 " " " " " " " CHCHCOOCH.sub.3 1-146 4-Cl-phenyl (CH.sub.2).s     ub.4 O O O F Cl CHCBrCOOCH.sub.3 1-147 " (CH.sub.2).sub.2 CH(F)CH.sub.2     " " " " " CHCHCOOCH.sub.3 1-148" " " " " " " CHC(CH.sub.3 )CH.sub.2     COOCH.sub.3 1-149 " (CH.sub.2).sub.4 " " " " " CH.sub.2 SCH.sub.3 1-150     " " " " " " " CH.sub.2 CO.sub.2      CH.sub.3 1-151 4-CN-phenyl (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " "     OCH(CH.sub.3).sub.2 1-152 4-CH.sub.3 SO.sub.2 -phenyl " " " " " " "     1-153 4-CF.sub.3 -phenyl " " " " " " " 1-154 3,4-Cl.sub.2 -phenyl " " "     " " " " 1-155 4-(CH.sub.3).sub.2 NSO.sub.2 -phenyl " " " " " " " 1-156     4-F-phenyl " " " " " " " 1-157 (CH.sub.3).sub.2 NCO-phenyl " " " " " " "     1-158 1-cyclohexenyl " " " " " "  " 1-159 (CH.sub.2).sub.4N " " " " " "     " 1-160 (CH.sub.2).sub.5N " " " " " " " 1-161 4-Cl-phenyl CH.sub.2     CH(F)CH(F)CH.sub.2 " " " " " " 1-162 " " " " " " " OCH.sub.3 1-163     4-Cl-phenyl CH.sub.2 CH(F)CH(F)CH.sub.2 O O O F Cl OCHCH.sub.3 CCH 1-164     " " " " " " " OCH.sub.2      CCH 1-165 CHCHCH.sub.2 " " " " " " OCH(CH.sub.3).sub.2 1-166 CH.sub.2CH     " " " " " " " 1-167 4-CH.sub.3 OCO-phenyl CH.sub.2 CH(F)(CH.sub.2).sub.2     " " " " " " 1-168 Cl.sub.3 CCHCl " " " " " " " 1-169 CH.sub.2CCH.sub.3 "     " " " " " " 1-170 CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 (CH.sub.2).sub.4 "     " " " " " 1-171 CH.sub.2 CCl.sub.3 " " " " " " " 1-172 Cl.sub.3      CC(CH.sub.3).sub.2 " " " " " " OCH(CH.sub.3).sub.2 1-173 ClCH.sub.2     CH.sub.2 " " " " " " " 1-174 4-Cl-phenyl CH.sub.2 CF.sub.2      (CF.sub.2).sub.2 " " " " " " 1-175 " CHCHSCH.sub.2 " " " " " " 1-176 "     (CH.sub.2).sub.2 CH(F) " " " " " 1-177 " (CH.sub. 2).sub.2 OCH.sub.2 " "     " " " " 1-178 " (CH.sub.2).sub.2 N(CH.sub.3)CH.sub.2 " " " " " " 1-179 " C     H.sub.2 CFCHCH.sub.2 " " " " " OCH.sub.2 CCH 1-180 " " " " " " "     OCH.sub.3 1-181 4-Cl-phenyl CH.sub.2      CFCHCH.sub.2 O O O Cl Cl OCH(CH.sub.3).sub.2 1-182 " CH.sub.2      CHCFCH.sub.2 " " " " " " 1-183 phenyl CH.sub.2 CFCFCH.sub.2 " " " " " "     1-184 CH.sub.2CH " " " " " " " 1-221 phenyl (CH.sub.2).sub.2 CHFCH.sub.2     " " " F Br " 1-222 " " " " " " " COOCH(CH.sub.3).sub.2 1-223 " " " " " "     CN OCH(CH.sub.3).sub.2 1-224 " " " " " " " COOCH(CH.sub.3).sub.2 1-225 "     " " " " " CH.sub.3 OCH(CH.sub.3).sub.2 1-226 " " " " " " " COOCH(CH.sub.3     ).sub.2 1-227 " " " " " " Cl CH(CH.sub.3).sub.2       Compd. R.sub.1 A X Y Z Ar       1-185 4-Cl-phenyl (CH.sub.2).sub.4 O O O 1-(2-propinyl)-5-F-benzo[d]pyr     azol-6-yl 1-186 " " " " " 4-CH.sub.3 -7-F-benzo[e]-1,3-dioxine-6-yl     1-187 " " " " " 2,2,5-tri-F-benzo[d]dioxole-6-yl 1-188 " " " " "     6-F-2,3-dihydro-benzo[b]-1,4-dioxin-7-yl 1-189 " " " " " 4-(2-propinyl)-7     -F-benzo[b]-1,4-thiazin-3-on-6-yl 1-190 " (CH.sub.2).sub.2 CH(F)CH.sub.     2 " " " 4-(2-propinyl)-7-F-Ar.sub.1 1-191 " (CH.sub.2).sub.4 " " "     4-allyl-7-F-Ar.sub.1 1-192 " (CH.sub.2).sub.2 CH(F)CH.sub.2 " " "     4-CH.sub.3 -7-F-Ar.sub.1 1-193 " (CH.sub.2).sub.4 " " " 4-(C.sub.2     H.sub.5 OOCCH.sub.2)-7-F-Ar.sub.1 1-194 " " " " " 4-(CH.sub.2      OCH.sub.2)-7-F-Ar.sub.1 1-195 " " " " " 4-(CNCH.sub.2)-7-F-Ar.sub.1     1-196 " " " " " 4-CH.sub.2 -(tetrahydropyran-4-yl)-7-F-Ar.sub.1 1-197 "     " " " " 4-CH.sub.2 -(5,6-dihydro-2H-thiin-3-yl)-7-F-Ar.sub.1 1-198 " " "     " " 4-CH.sub.2      (2-pyridyl)-7-F-Ar.sub.1 1-199 " " " " " 4-(pyrazin-2-yl-methyl)-7-F-Ar.     sub.1 1-200 " " " " " 4-(1,2-oxazole-3-yl-methyl)-7-F-Ar.sub.1 1-201 " "     " " " 4-(5-CH.sub.3 -1,2,4-oxdiazol-3-yl-methyl)-7-F-Ar.sub.1 1-202     4-Cl-phenyl (CH.sub.2).sub.4 O O O 1-(2-propinyl-6-F-Ar.sub.2 1-203 " "     " " " 1-allyl-6-F-Ar.sub.2 1-204 " (CH).sub.2      CHFCH.sub.2 " " " 1-(2-propinyl)-6-F-Ar.sub.3 1-205 " " " " " 1-allyl-6-     F-Ar.sub.3 1-206 " " " " " 1-allyl-6-F-quinoline-2(1H)-on-7-yl 1-207 " "     " " " 3-(2-propinyl)-6-F-benzo[d]-1,3-oxazole-2(3H)-on-5-yl 1-208 "     (CH.sub.2).sub.4 " " " 3-(2-pyridyl-CH.sub.2)-6-F-Ar.sub.4 1-209 " " " "     " 3-(1,2-oxazole-3-yl-CH.sub.2)-6-F-Ar.sub.4 1-210 " " " " " 5-F-1-CH.sub     .3      indol-6-yl 1-211 " " " " " 6-F-chroman-7-yl 1-212 " " " " " 5-F-2,3-dihy     drobenzo[b]furan-6-yl 1-213 " " " " " 5-F-indan-1-on-6-yl 1-214 " " " "     " 7-F-4-isopropyl-chromen-2-on-6-yl 1-215 " " " " " 5-F-1-(2-propinyl)-1-     H-indol-2,3-dion-6-yl 1-216 " " " " " 5-F-benzo[d]imidazol-2(1H,3H)-on-6-     yl 1-217 " " " "  " 5-F-1,3-di(CH.sub.3)-1,3-dihydro-indol-2-on-6-yl     1-218 " " " " " 1-allyl-5-F-1,3-dihydro-indol-2-on-6-yl 1-219 " (CH.sub.2     ).sub.2      CHFCH.sub.2 " " " 6-F-1(2-propinyl)-3,4-dihydroquinolin-2(1H)-on-7-yl     1-220 " " " " " 1-(2-propinyl)-5-F-benzo[d]-1,2,3-triazol-6-yl

Key to Abbreviations

(1) isomeric mixture of 4- and 5-substituted compound

(2) Ar=2-R₂ -4-R₃ -5-R₄ -phenyl

(3) Ar₁ =2-R₂ -4-dihydro-benzo[b]-1,4-oxazin-3-on-6-yl

(4) Ar₂ =3,4-dihydro-2H-quinoxalin-2-on-7-yl

(5) Ar₃ =1 H-quinoxalin-2-on-7-yl

(6) Ar₄ Benzo[d]-1,3-thiazol-2(3H)-on-5-yl

(7) numbering convention ##STR9##

EXAMPLE 2-13[[(4-chloro-2-fluoro-5-isopropoxyphenyl)aminojcarbonyl-4-thiomorpholinecarboxylic acid phenyl ester-1,1 dioxide

To 2.25 g (0.005 mol) of3[[(4-chloro-2-fluoro-5-isopropoxyphenyl)-aminolcarbonyl-4-thiomorpholinecarboxylicacid-phenyl ester in 20 ml of methylene chloride (CH₂ CH₂) is addeddropwise, without cooling a dried (Na₂ SO₄) solution of 4 g ofm-chloro-perbenzoic acid (55%/˜0.013 mol) in 200 ml of CH₂ CH₂. Afterthe exothermic (28°) reaction has subsided, the reaction solution isstirred 16 hours longer at ambient temperature and is then washed with140 ml of water, which contains 14 g of KHCO₃ and 2 g of NaHSO₃. Thenthe organic layer is separated, washed with water (150 ml), dried (Na₂SO₄) and evaporated in vacuo. The residue is chromatographed on a silicagel column.

Elution with ethyl acetate affords the title compound, which ishomogenous by TLC (Rf=0.31 on silica gel with ethyl acetate-hexane 1:1).

In an analogous manner, the folloving compounds of formula (I) set forthin Table 2 are made.

                                      TABLE 2                                     __________________________________________________________________________     ##STR10##                                                                    Compd.                                                                             R.sub.1                                                                           A         X Y Z R.sub.2                                                                         R.sub.3                                                                         R.sub.4     m.p. or R.sub.f on silica            __________________________________________________________________________                                             gel                                  2-2  phenyl                                                                            (CH.sub.2).sub.2 SO.sub.2 CH.sub.2                                                      O O O F Cl                                                                              OCH.sub.3   74-76°                        2-3  "   "         " " " " " OCH.sub.2 CH.sub.3                                                                        0,35 (ethyl acetate-hexane 1:1)      2-4  "   "         " " " " " OCH.sub.2 CH.sub.2 CH.sub.3                                                               0.35 (ethyl acetate-hexane 1:1)      2-5  "   "         " " " " " OC.sub.4 H.sub.9 -sec.                                                                    0,38 (ethyl acetate-hexane 1:1)      2-6  "   "         " " " " " OC.sub. 5 H.sub.9 -cycl.                                                                  0,37 (ethyl acetate-hexane 1:1)      2-7  "   "         " " " " " OCH.sub.2 CCH                                                                             129-131°                      2-8  "   "         " " " " " OCH(CH.sub.3)CCH                                                                          0,58 (ethyl acetate)                 2-9  CH.sub.3                                                                          "         " " " " " OCH(CH.sub.3).sub.2                                                                       168-169°                      2-10 "   "         " " " " " OCH(CH.sub.3)CCH                                                                          R.sub.f = 0,47 (ethyl                __________________________________________________________________________                                             acetate)                         

EXAMPLE 3-13[[(4-Chloro-2-fluoro-5-isopropoxyphenyl)azinolearbonyl]-4-thiomorpholine carboxylic acid methyl ester-1-oxide

To 13,3 g (0,034 mol) of3[[(4-chloro-2-fluoro-5-isopropoxyphenyl)amino]carbonyl]-4-thiomorpholinecarboxylicacid-methyl ester in 150 ml of dry methylene chloride is added dropwisewith stirring the dried (Na₂ SO₄) solution of 7,25 g m-chloroperbenzoicacid (80 %; 0,034 mol) at such a rate, that the temperature does notrise above 5°. After being kept at 50 for 20 hours, the reactionsolution is washed with 500 ml of water which contains 50 g of NaHCO₃and 5 g of NaHSO₃.

Then the organic layer is separated, washed with water (250 ml), dried(Na₂ SO₄) and evaporated in vacuo.

The residue is chromatographed on a silica gel column.

Elution with ethyl acetate affords the title compound as a reddishamorphous solid which is homogeneous by TLC (Rf=0,07 on silica gel withethyl acetate).

In an analogous manner, the following compounds set forth in Table 3 aremade.

                                      TABLE 3                                     __________________________________________________________________________     ##STR11##                                                                    Compd.                                                                        No.  R.sub.1                                                                           A         X Y Z R.sub.2                                                                         R.sub.3                                                                         R.sub.4     m.p. or Rf on silica                 __________________________________________________________________________                                             gel                                  3-2  phenyl                                                                            (CH.sub.2).sub.2 SOCH.sub.2                                                             O O O F Cl                                                                              OCH(CH.sub.3).sub.2                                                                       152-154°                      3-3  "   "         " " " " " OCH.sub.2 CCH                                                                             113-115°                      3-4  "   "         " " " " " OCH(CH.sub.3)CCH                                                                          R.sub.f = 0.13 (ethylacetate)        3-5  CH.sub.3                                                                          "         " " " " " OCH(CH.sub.3).sub.2                                                                       R.sub.f = 0.08                       __________________________________________________________________________                                             (ethylacetate)                   

INTERMEDIATES EXAMPLE 4-1 Pipecolic acid 4-chloro-2-fluoro-5-isopropoxyanilide

To a suspension of 18.4 g (0.1 mol) pipecolic acid chloridehydrochloride in 400 ml methylenechloride are added 20.3 g (0.1 mol)4-chloro-2-fluoro-5-isopropoxy aniline. After the exothermic (30° C.)reaction has subsided, 18 g NaHCO3 are added and the reaction mixture isstirred for 30 minutes at room temperature. 30 ml of water is added andstirring is continued for 1 hour. After the addition of 200 ml water theorganic phase is separated, washed with 100 ml water, dried (MgSO₄) andevaporated in vacuo. After treatment of the residue with pentane thecompound is obtained in form of white crystals. Mp. 960° C.

In an analogous manner, the following compounds of formula (II) setforth in Table 4 are made.

                                      TABLE 4                                     __________________________________________________________________________     ##STR12##                                                                     Compound                                                                            ##STR13##   R.sub.2                                                                         R.sub.3                                                                          R.sub.4                                                                               mp or R.sub.f                                 __________________________________________________________________________    4-2   piperid-2-yl                                                                              F Cl H        88° C.                                 4-3   "           " "  OCH.sub.2 CH.sub.3                                                                     88° C.                                 4-4   "           " "  OH.sub.2 CH.sub.2 CH.sub.3                                                             89° C.                                 4-5   "           " "  OCH.sub.3                                                                             142° C.                                 4-6   "           " "  OCH(CH.sub.3).sub.2                                                                    94° C.                                 4-7   "           " "  OCHCOOEt                                                                              R.sub.f = 0,1(Ether)                                                  CH.sub.3                                               4-8   "           " "  OCOOCH.sub.3                                                                          126° C.                                 4-9   "           H "  COOCH.sub.2 CH.sub.3                                                                  109° C.                                 4-10  1,2,3,6-tetrahydro-                                                                       F "  OCH(CH.sub.3).sub.2                                                                    71° C.                                       pyridin-2-yl                                                            4-11  1,4-thiomorpho-                                                                           " "  "        84° C.                                       lin-3-yl                                                                4-12  2,3-dehydro-1,4-                                                                          " "  "                                                            thiomorpholin-3-yl                                                      4-13  3-F-piperidin-2-yl                                                                        F Cl OCH(CH.sub.3).sub.2                                    4-14  4-F-piperidin-2-yl                                                                        " "  "                                                      4-15  5-F-piperidin-2-yl                                                                        " "  "                                                      4-16  4,4-di-F-piperidin-2-yl                                                                   " "  "                                                      4-17  5,5-di-F-piperidin-2-yl                                                                   " "  "                                                      4-18  4-F-1,2,3,6-tetrahydro-                                                                   " "  "                                                            pyridin-2-yl                                                            4-19  5-F-1,2,3,6-tetrahydro-                                                                   " "  "                                                            pyridin-2-yl                                                            4-20  4,5-di-F-1,2,3,6-                                                                         F Cl OCH(CH.sub.3).sub.2                                          tetrahydro-pyridin-2-yl                                                 4-21  4,5-di-F-piperidin-2-yl                                                                   " "  "                                                      4-22  3,3-di-F-piperidin-2-yl                                                                   " "  "                                                      __________________________________________________________________________

Biology

The herbicidal activity of the compounds of this application isdemonstrated by experiments carried out for the pre-emergence andpost-emergence control of a variety of weeds. Such weeds includeAbutilon theophrasti, Amaranthus retroflux, Sinapis alba, Solanumnigrum, Bromus tectorum, Setaria viridis, Avena fatua, and Echinochloacrus-galli.

In preemergence testing, small plastic greenhouse pots filled with drysoil are seeded with the various weed seeds. Twenty-four hours or lessafter the seeding, the pots are sprayed with water until the soil is wetand the test compounds formulated as aqueous emulsions of acetonesolutions containing emulsifiers are sprayed at the indicatedconcentrations emulsifiers are sprayed on the surface of the soil. Afterspraying, the soil containers are placed in the greenhouse and providedwith supplementary heat as required and daily or more frequent watering.The plants are maintained under these conditions for a period of from 14to 21 days, at which time the conditions of the plants and the degree ofinjury to the plants is rated.

In post-emergence testing, the compounds to be tested are formulated asaqueous emulsions and sprayed on the foliage of the various weed speciesthat have attained a prescribed size. After spraying, the plants areplaced in a greenhouse and watered daily or more frequently. Water isnot applied to the foliage of the treated plants. The severity of theinjury is determined 21 days after treatment and is rated.

In general, the compounds of this application demonstrate good activityagainst most of the weed varieties noted above. They are particularlyactive against Abutilon theophrasti and Solanum nigrum, in both pre- andpost-emergence testing.

What is claimed is:
 1. A compound of the formula (I) ##STR14## wherein Ris H, C₁₋₃ alkyl or C₂₋₃ alkenyl optionally substituted by halo; or isC₂₋₃ alkinyl;R₁ is phenyl(C₁₋₄ alkyl)_(n), wherein the phenyl group isoptionally substituted by one or more groups selected from--C(O)--O--C₁₋₄ alkyl, C₁₋₈ alkyl, C₁₋₈ haloalkyl, halo, nitro, cyano,--SO₂ C₁₋₄ alkyl, SO₂ NR₅ R₅ ' and S(O)NR₅ R₅ '; or is C₅₋₈cycloalkenyl; --N═R₆ ; C₂₋₈ alkenyl, C₁₋₈ alkyl or C₃₋₅ alkinyloptionally substituted with one or more halo; or is C₁₋₄ alkyl--SO₂--C₁₋₄ alkyl; R₂ is halo or hydrogen; R₃ is halo, cyano or C₁₋₄ alkyl;R₄ is H; NO₂ ; NH₂ ; CN; C₁₋₈ alkyl optionally substituted by CN; C₂₋₈alkenyl optionally substituted by CN; C₂₋₅ alkinyl; (C₂₋₅alkoxycarbonyl)-C₁₋₄ alkyl, whereby the carbon atom of the alkyl groupalpha to the alkoxycarbonyl group may bear one more C₂₋₅ alkoxcarbonylgroups or a cyano group; (C₂₋₅ alkoxycarbonyl)-C₋₄ alkoxy-C₁₋₄ alkyl;(C₂₋₅ alkoxycarbonyl)-C₁₋₄ alkylamino-C₁₋₄ alkyl; (C₂₋₅alkoxycarbonyl)-C₂₋₅ alkenyl, whereby the alkenyl moiety is optionallysubstituted by halogen; C₁₋₄ alkylthio-C₁₋₄ alkyl; C₁₋₄alkylsulfonyl-C₁₋₄ alkyl; C₁₋₄ alkoxy-C₁₋₄ alkoxy; X(Alk)_(m) R₇ ;OCH(SR₈)-COOR₉ ; NR₁₀ R₁₁ ; COOR₁₂ ; CONR₁₃ R₁₃ '; COR₁₄ or R₁₅ ; or R₃and R₄ join together with the phenyl ring to form a bicyclic ringcontaining nine to ten ring atoms, one to three of said ring atomsoptionally being selected from oxygen, nitrogen and sulfur, andoptionally being substituted with one or more groups selected from C₃₋₈alkinyl, C₁₋₈ alkyl, halo, oxo, C₁₋₄ alkylene-R₁₆, and C₂₋₈ alkenyl; R₅and R₅, independently are C₁₋₄ alkyl; R₆ is C₂₋₈ alkylidene; R₇ is H;C₁₋₄ alkyl, C₂₋₅ alkenyl C₂₋₅ alkinyl, or C₃₋₈ cycloalkyl, whichhydrocarbyl is unsubstituted or substituted by one or more halogen or byCN; cyclopentanonyl; phenyl optionally substituted by O--Alk'--COOR₈ ;or is C₂₋₅ alkanoyl; C₂₋₅ alkoxycarbonyl; C₂₋₈ (alkoxycarbonyl)(C₃₋₈cycloalkyloxy)-carbonyl, in which the alkoxy or cycloalkyloxy group isoptionally substituted by one or more halo; CONR₉ R_(8'),C(═NOR₈)-COOR_(8'), CN; P(O)(OR₈)(OR_(8')) or R₁₅ ; R₈ and R₈,independently are C₁₋₄ alkyl; R₉ is C₁₋₄ alkyl optionally substituted byone or more halo; R₁₀ is H or C₁₋₄ alkyl; R₁₁ is H; C₁₋₄ alkyl,optionally substituted by P(O)(OR₈)(R_(8')); C₂₋₅ alkanoyl; C₂₋₅alkoxycarbonyl; or C₂₋₅ alkoxycarbonyl-C₁₋₄ alkyl; R₁₂ is N═(C₂₋₈alkylidene); C₁₋₄ alkyl optionally substituted by one or more groupsselected from halo, C₁₋₄ alkoxy, tri-C₁₋₄ alkylsilyloxy, tri-C₁₋₄alkyl-silyl, (tri-C₁₋₄ alkylsilyloxy)-carbonyl, C₂₋₅ alkoxycarbonyl,P(O)(OR₈)(OR_(8')), C₂₋₅ alkanoyl-oxy or by di(C₁₋₄alkylamino)-carbonyloxy in which both alkyl groups may be tied togetherto form a saturated 5 to 6 membered heteroring optionally containing onefurther heteroatom selected from O, S and N, and in which any furtherN-heteroatom present may, depending on the hydrogenation degree of theheteroring, bear a hydrogen or a C₁₋₄ alkyl group; R₁₃ is H or C₁₋₄alkyl; R₁₃, is H, C₁₋₄ alkyl optionally substituted by halo, C₁₋₄alkoxy, phenyl, CHO, C₂₋₅ alkanoyl, C₁₋₄ alkylsulfonyl, (C₂₋₅alkoxycarbonyl)-C₁₋₄ alkyl or(C₂₋₅ alkoxycarbonyl)-C₁₋₄ alkoxy; or R₁₃and R₁₃, together form a 4 to 6 membered heteroring optionallycontaining one or two further heteroatoms selected from O, S and N,whereby, depending on the hydrogenation degree of the heteroring, anyfurther N-heteroatom may bear hydrogen or be substituted by C₁₋₄ alkyl;R₁₄ is H or C₁₋₄ alkyl; R₁₅ is a heterocyclic ring having 5 or 6 ringatoms, one to three of said ring atom being selected from oxygen, sulfurand nitrogen, which ring is optionally substituted with one or more C₁₋₄alkyl groups; R₁₆ is CN; COOR₁₂ ; OC₁₋₄ alkyl; or is4-tetrahydropyranyl, 2H-5,6-dihydro-thiin-3-yl, 2-pyridyl, 2-pyrazinyl,1,2-oxazol-3-yl, or 1,2,4-oxdiazol-3-yl, each of which is optionallysubstituted with C₁₋₄ alkyl; Alk and Alk' independently are C₁₋₄alkylene; n and m independently are 0 or 1; A is a C₃₋₄ alkylene orstraight chain substituted by one to three halogen; and X, Y and Z areindependently selected from O and S.
 2. A compound of formula (I)according to claim 1 wherein X, Y and Z are oxygen and R is H.
 3. Acompound of formula (I) according to claim 1 wherein A is straight chainbutylene substituted by fluorine.
 4. A compound of formula (I) accordingto claim 2 wherein R₂ is chlorine or fluorine and R₃ is CN, Br, Cl ormethyl.
 5. A compound of formula (I) according to claim 3 wherein R₂ ischlorine or fluorine and R₃ is CN, Br, Cl or methyl.
 6. A compound offormula (I) according to claim 4 wherein R₁ is selected from the groupconsisting of phenyl optionally substituted with halogen, nitro or CH₃OC(O)--; C₁₋₄ alkyl optionally substituted with one to four halogenatoms; C₂₋₄ alkenyl; and C₂₋₃ alkylidene═N--.
 7. A compound of formula(I) according to claim 5 wherein R₁ is selected from the groupconsisting of phenyl optionally substituted with halogen, nitro or CH₃OC(O)--; C₁₋₄ alkyl optionally substituted with one to four halogenatoms; C₂₋₄ alkenyl; and C₂₋₃ alkylidene═N--.
 8. A compound of formula(I) according to claim 6 wherein R₄ is O(Alk)_(m) R₇, COOR₁₂ or CONR₁₃R_(13'), R₇ is C₁₋₄ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkinyl or C₂₋₅alkoxycarbonyl, R₁₂ is C₁₋₄ alkyl optionally substituted by halo, R₁₃ isH and R₁₃, is C₁₋₄ alkyl optionally substituted by halo.
 9. A compoundof formula (I) according to claim 7 wherein R₄ is O(Alk)_(m) R₇, COOR₁₂or CONR₁₃ R_(13'), R₇ is C₁₋₄ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkinyl or C₂₋₅alkoxycarbonyl, R₁₂ is C₁₋₄ alkyl optionally substituted by halo, R₁₃ isH and R₁₃, is C₁₋₄ alkyl optionally substituted by halo.
 10. Aherbicidal composition comprising a compound of formula (I) as definedin claim 1 and an agriculturally acceptable carrier.
 11. A compound ofthe formula (II) ##STR15## wherein R--R₄, A and Z are as defined inclaim
 1. 12. A method of combatting weeds which comprises applying tothe weeds or their locus a herbicidally effective amount of the compounddefined in claim 1.